Halotriazinylmonoazo dyestuffs

ABSTRACT

A WATER SOLUBLE MONAZO DYESTUFF CONTAINING A SINGLE ACIDIC WATER SOLUBILIZING GROUP AND HAVING THE FORMULA   1-(A-N=N-B-NH-),3-(HAL-),5-Y-S-TRIAZINE   WHEREIN A IS A PHENYL OR NAPHTHYL NOIETY CONTAINING A SINGLE ACIDIC WATER-SOLUBILIZING GROUPF B IS   (1) -(2-R1,5-R2-1,4-PHENYLENE)- OR   SP   (2) -(1,4-NAPHTHYLENE)-   R1 IS H, METHYL, METHOXY OR ACYLAMIDO; R2 IS H, METHYL OR METHOXY; HAL IR CL OR BR; Y IS NHR3, SR4 OR OR5; AND R3, R4 AND R5 ARE INDIVIDUALLY H, ALKYL OR PHENYL, A METHOD OF DYEING NITROGENOUS FIBERS THEREWITH

United States Patent 3,565,882 HALOTRIAZINYLMONOAZO DYESTUFFS Nagib A.Doss, Loudonville, N.Y., assiguor to GAF Corporation, New York, N .Y., acorporation of Delaware No Drawing. Filed Dec. 18, 1967, Ser. No.691,134 Int. Cl. C09b 62/08 U.S. Cl. 260-153 7 Claims ABSTRACT OF THEDISCLOSURE A water soluble monazo dyestulf containing a single acidicwater solubilizing group and having the formula N-C-Hal wherein A is aphenyl or naphthyl moiety containing a single acidic water'solubilizinggroup; B is R is H, methyl, methoxy or acylamido; R is H, methyl ormethoxy; Hal is C1 or Br; Y is NHR SR or CR and R R and R areindividually H, alkyl or phenyl, A method of dyeing nitrogenous fiberstherewith.

This invention relates to new monazo dyestuffs, and more particularly tosuch dyestuffs containing only one water solubilizing group and onemonohalotriazinyl group, and a method for dyeing nitrogenous fiberstherewith.

Many dyestuffs have been disclosed in the prior art which are of the azotype and contain halotriazinyl radicals. Such dyestuffs are for the mostpart intended to be employed as fiber-reactive dyestuffs by applicationto cellulosic materials in the presence of alkali. US. Pat. No.2,945,022 discloses monoazo and disazo dyestuffs containing amonohalotriazinyl radical and at least two strongly acid watersolubilizing groups, and are applied to cellulosic materials in thepresence of alkali. Such dyestuffs have however not been found to beparticularly suited for dyeing nitrogenous fibers in the disclosedmanner.

It is an object of this invention to provide dyestuffs which will not besubject to one or more of the above disadvantages. Another object ofthis invention is the provision of novel dyestuffs suitable for dyeingnitrogenous fibers. Still another object of the invention is theprovision of a method for dyeing nitrogenous fibers with such dyestuffs.Other objects and advantages will become apparent as the descriptionproceeds.

The attainment of the above objects is made possible by this inventionwhich includes the provision of novel dyestuffs of Formula I above, anda method for dyeing nitrogenous materials, particularly fibrousmaterial, therewith.

These dyestuffs of the invention are characterized by yielding excellentdyeings on nitrogenous fibers, especially nylon, having bright, fullshades of excellent light and wash fastness properties.

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In the above Formula I, A represents the residue of a diazotizablearomatic amine of the phenyl and naphthyl series containing a singleacidic solubilizing group which is preferably a sulfonic acid group butmay be a carboxylic acid group. The acylamido value for R may bealiphatic or aromatic such as acetamido, propionamido, benzoylamido orthe like. The alkyl value for R R and R may be straight or branched andof any number of carbon atoms although lower alkyl groups of l to 4carbon atoms are preferred. In general, the A moiety and the phenylvalue for Y may if desired contain similar lower alkyl and/or loweralkoxy substituents of 1 to 4 carbon atoms. Similarly, the H atomsbonded to N atoms shown in the definition of said formula I may bereplaced by lower alkyl of 1 to 4 carbon atoms.

The dyestuffs of this invention may be prepared in conventional manner.Other such method involves diazotization of a diazotizable aromaticamine of the formula (II) A 2 and coupling the diazotized amine with anapproximately equivalent amount of a coupling component of the formula(III) BNH followed by condensing the resulting monoazo dyestufi with anapproximately equivalent amount of the primary condensation product ofcyanuric chloride or bromide with ammonia, an amine of the formula (IV)HNHR a thiol of the formula HSR or an alcohol of the formula (VI) HORand which condensation product has the formula (VII) N=CHalAlternatively, the same dyestuff may be reacted with cyanuric chlorideor bromide and one of the two triazinyl halogens replaced with a Y groupby reaction with an equivalent amount of ammonia, or an amine, thiol oralcohol of Formula IV, V or VI above.

As representative diazotizable aromatic amines of the Formula II above,there may be mentioned orthanilic acid metanilic acid sulfanilic acid4-chlorometanilic acid 6-chlorometanilic acid 3-chlorosulfani1ic acid4-amino-o-toluenesulfonic acid S-amino-o-toluenesulfonic acid4-methoxymetanilic acid 6-rnethoxymetanilic acid S-methoxyorthanilicacid aminobenzoic acid 4-amino-2-naphthalenesulfonic acid4-amino-l-naphthalenesulfonic acid S-arnino-l-naph-thalenesulfonic acid5-amino-2-naphthalenesulfonic acid 8-amino-2-naphthalenesulfonic acid7-amino-l-naphthalenesulfonic acid 6-amino-2-naphthalenesulfonic acid.

As representative coupling components of Formula III above, there may bementioned aniline o-toluidine m-toluidine o-anisidine m-anisidine2,5-dimethoxyaniline S-methyl-o-anisidine 3-benzoylamido or -acetamidoaniline l-aminonaphthalene N-methyl-l-naphthylamineN-ethyll-naphthylamine.

As representative Y values insertable by reaction of the triazinylhalogen atom with ammonia or a compound of Formula IV, V or VI above,there may be mentioned lower alkyl amines such as rnethylamine,dimethylamine, ethylamine, diethylamine, propylamine, butyl amine;arylamines such as aniline, the toluidines, the anisidines, thecresidines and the like; alkoxy such as methoxy, ethoxy, propoxy,butoxy; aryloxy such as phenyloxy, tolyloxy, anisyloxy; thio derivativessuch as methylthio, ethylthio, propylthio, butylthio, phenylthio and thelike.

The dyestuffs of this invention are highly advantageous for dyeingnitrogenous organic polymers of natural or synthetic origin in any formsuch as in bulk or in shaped solid form such as films, fibers andfilaments, and other articles. They are especially suitable for coloringnitrogenous fibers, particularly those containing repeating amide groupsin the polymer chain, as for example W001, silk, synthetic linear superpolyamides such as Nylon 6 and 66 and polypyrrolidone, and polyurethanesof either the ordinary type such as from polyethylene adipate andtolylene diisocyanate, or the segmented spandex type such as frompolyethylene oxide molecular weight 1000, tolylene or hexamethylenediisocyanate and propyleneglycol.

In general, the aforementioned nitrogenous materials may be colored bytreatment in a Weakly acid, neutral or weakly basic aqueous dye bath,for example having a pH of about 5 to 9, at an elevated temperature ofat least about 150 F. up to the boil containing about 0.3 to 4% of oneor more dyestulfs of the invention O.W.F. (on the weight of the fiber).Other usual dyeing assistants may of course be employed. The dyeing isthen simply rinsed and dried.

The following examples are only illustrative of preferred embodiments ofthe invention and are not to be regarded as limitative. All parts andproportions referred to herein and in the appended claims are by weightunless otherwise indicated.

EXAMPLE 1 O OH;

I /N=C G1 N=CNHz S 0 3H C Ha A 12.4 g. sample of the dyestuff preparedby coupling diazotized 6-chlorometanilic acid to S-methyl-o-anisidine isadded to 800 g. of water at C. It is stirred to a smooth slurry and thepH adjusted to about 8 with caustic soda solution. It is clarified by aNuchar (activated carbon) treatment, and iced to 0 C. with ice. To thisis then added 33.5 g. of cyanuric chloride in g. of acetone. Afterstirring at 05 C. for 15 minutes, the pH is gradually raised over a 23hour period to about 7 at a temperature not over about 5C. 45 g. ofammonium hydroxide 26 B. is added. It is stirred for 1 hour, thetemperature gradually raised to about 35 C. It is salted with 5% byvolume salt solution, stirred overnight, filtered, Washed and dried. Ayellow dye is obtained which has excellent properties as a polyamide,polyurethane, wool, and silk dye.

In the same manner as in Example 1, the following dyes are prepared,corresponding to Formulae I, II and III above.

Color on Example Diazotizable amine (A-NHz) Coupler (B=NH2) Hal. Y nylon44 4-aminosalicylic acid Aniline 01 I\ HCH3 Yellow 45 do "d Cl NI'ICQII5Do. 46 do do Cl -OCH3 Do. 47-.. -d0 do-. Cl SCH Do. 48 do d0 Bi NH Do.49.. N aphthionie acid (l-amino- -dimethoxyaniline 01 NH; Orange.

naphthalenet-sulfonic) 50 d0 d0 Cl -NHCGH Do. 51 5-amino-2-naphthalened0Ol -NH Do.

sulfonic acid. 52 .do d0 Cl NI-ICBH Do. 53 8-amino-2-naphthalene- ...d0Cl Nl-I2 Do.

sulionic acid.

Cl NHCeI-I Do. 1 NH; Do. 01 NHCeH D0. 3-acetan1id0 aniline l H Do.3-benzoyla1nido aniline Cl NH Do. o-anisidine Cl -NH Yellon NI1C1QH1 DO.H Do. --OH D0.

EXAMPLE 63 or An aqueous dyebath is prepared containing 1% of the dye ofExample 1 O.W.F. and 4% ammonium sulfate O.W.F. A swatch of Nylon-66 isdyed in this solution at or near the boil for 1 hour, rinsed and dried.The nylon 1 had which i fast to 1. ed 1. 3 f fi g yel OW s e S R is H,methyl, methoxy, lower alkanoylarnido, or

1g was 111,, a 11 g benzoylamido;

EXAMPLE 64 R is H, methyl or methoxy;

Hal is C1 or Br;

An aqueous dyebath was prepared to contain 1.0% of the dye of Example 1O.W.F., 15.0% sodium sulfate O.W.F., and 6.0% ammonium sulfate O.W.F.Wool is dyed in this bath at the boil for 1 hour, rinsed and dried. Thewool is dyed a level greenish yellow shade which is fast to light,washing and fulling.

This invention has been disclosed with respect to certain preferredembodiments, and it will be understood that modifications and variationsthereof will become obvious to persons skilled in the art and areintended to be included within the spirit and purview of thisapplication and the scope of the appended claims.

I claim:

1. A water soluble monoazo dyestufi for dyeing nylon containing a singleacidic water-solubilizing group selected from the class consisting ofsulfonic acid and carboxylic acid moieties and having the formulawherein A is phenyl, naphthyl, or C alkyl or alkoxy substituted phenylor naphthyl containing a single acidic Water-solubilizing group; B is Yis NHR SR or 0R and R R and R are individually H, C alkyl or phenyl.

2. A dyestufi as defined in claim 1 wherein said water solubilizinggroup is a sulfonic acid group.

3. A dyestuif as defined in claim 1 wherein A is 4- chloro-3-sufophenyl,B is (1), R is CH R is OCH Hal is Cl, and Y is NH 4. A dyestuif asdefined in claim 1 wherein A is 3- sulfophenyl, B is (1), R is H, R isOCH Hal is Cl, and Y is NH 5. A dyestuff as defined in claim 1 wherein Ais 6- methyl-3-sulfophenyl, B is (1), R is CH R is OCH Hal is Cl and Yis NH 6. A dyestuff as defined in claim 1 wherein A is 4- sulfonaphthyl,B is (1), R and R are each OCH Hal is Cl and Y is NH 7. A dyestuii asdefined in claim 1 wherein A is 2- sulfophenyl, B is (1), R is H, R isOCH Hal is Cl and Y is NH References Cited UNITED STATES PATENTS2,945,022 7/1960 Fisciatiet a1 260153 CHARLES B. PARKER, PrimaryExaminer D. M. PAPUGA, Assistant Examiner US. Cl. X.R. 8--41, 54, 55

